Synthesis of Terpyridine-Terminated Amphiphilic Block Copolymers and Their Self-Assembly into Metallo-Polymer Nanovesicles

Tatyana Elkin; Stacy M Copp; Ryan L Hamblin; Jennifer S Martinez; Gabriel A Montaño; Reginaldo C Rocha

doi:10.3390/ma12040601

Synthesis of Terpyridine-Terminated Amphiphilic Block Copolymers and Their Self-Assembly into Metallo-Polymer Nanovesicles

Materials (Basel). 2019 Feb 17;12(4):601. doi: 10.3390/ma12040601.

Authors

Tatyana Elkin¹, Stacy M Copp², Ryan L Hamblin³, Jennifer S Martinez^{4

5}, Gabriel A Montaño^{6

7}, Reginaldo C Rocha⁸

Affiliations

¹ Los Alamos National Laboratory, Center for Integrated Nanotechnologies, Los Alamos, NM 87545, USA. tatyana_elkin@lanl.gov.
² Los Alamos National Laboratory, Center for Integrated Nanotechnologies, Los Alamos, NM 87545, USA. smcopp@lanl.gov.
³ Los Alamos National Laboratory, Center for Integrated Nanotechnologies, Los Alamos, NM 87545, USA. rhamblin@lanl.gov.
⁴ Los Alamos National Laboratory, Center for Integrated Nanotechnologies, Los Alamos, NM 87545, USA. jennifer.martinez@nau.edu.
⁵ Center for Materials Interfaces in Research and Applications and Program of Applied Physics and Materials Science, Northern Arizona University, Flagstaff, AZ 86011, USA. jennifer.martinez@nau.edu.
⁶ Los Alamos National Laboratory, Center for Integrated Nanotechnologies, Los Alamos, NM 87545, USA. gabriel.montano@nau.edu.
⁷ Center for Materials Interfaces in Research and Applications and Program of Applied Physics and Materials Science, Northern Arizona University, Flagstaff, AZ 86011, USA. gabriel.montano@nau.edu.
⁸ Los Alamos National Laboratory, Center for Integrated Nanotechnologies, Los Alamos, NM 87545, USA. rcrocha@lanl.gov.

Abstract

Polystyrene-b-polyethylene glycol (PS-b-PEG) amphiphilic block copolymers featuring a terminal tridentate N,N,N-ligand (terpyridine) were synthesized for the first time through an efficient route. In this approach, telechelic chain-end modified polystyrenes were produced via reversible addition-fragmentation chain-transfer (RAFT) polymerization by using terpyridine trithiocarbonate as the chain-transfer agent, after which the hydrophilic polyethylene glycol (PEG) block was incorporated into the hydrophobic polystyrene (PS) block in high yields via a thiol-ene process. Following metal-coordination with Mn²⁺, Fe²⁺, Ni²⁺, and Zn²⁺, the resulting metallo-polymers were self-assembled into spherical, vesicular nanostructures, as characterized by dynamic light scattering and transmission electron microscopy (TEM) imaging.

Keywords: metallo-polymer; polymersome; self-assembly; terpyridine.

Abstract

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